Process for producing an opaque inorganic-organo titanate polymeric film

ABSTRACT

ORIENTED OPAQUE ULTRATHIN FILMS COMPRISING THERMOPLASTIC POLYMERS CONTAINING UP TO ABOUT 60 PARTS BY WEIGHT OF AN INORGANIC FILLER-ORGANO TITANATE COMPOUND ARE PREPARED BY EXTRUDING THE COMPOSITIONS AS FILMS AND THEREAFTER DRAWING THE RESULTANT FILMS AT A TEMPERATURE BELOW THAT AT WHICH THE FILMS REMAIN TRANSLUCENT. THE FILMS OF OUR INVENTION ARE USEFUL AS PACKAGING MATERIAL IN PREPARING ULTRATHIN PAPER, AND IN LAMINATES, NON-WOVEN FABRIC, RUG BACKING AND MESH STRUCTURES.

United States Patent Office 3,804,937 Patented Apr. 16, 1974 No Drawing.Original application Oct. 30, 1969, Ser. No. 872,757, now Patent. No.3,697,475. Divided and this application May 18, 1972, Ser. No. 254,803

Int. Cl. B29d 7/24; D01f 1/02 US. Cl. 264-211 3 Claims ABSTRACT OF THEDISCLOSURE Oriented opaque ultrathin films comprising thermoplasticpolymers containing up to about 60 parts by weight of an inorganicfiller-organo titanate compound are prepared by extruding thecompositions as films and thereafter drawing the resultant films at atemperature below I that at which the films remain translucent. Thefilms of our invention are useful as packaging material in preparingultrathin paper, and in laminates, non-woven fabric, rug backing andmesh structures.

This is a division, of application Ser. No. 872,757, filed Oct. 30, 1969and now issued as US. Pat. 3,697,475.

BACKGROUND OF THE INVENTION (a) Field of the invention (b) Descriptionof the prior art Paper has been made conventionally by felting naturallyoccurring cellulosic fibes such as cotton and wood. To producecellulosic paper of publication grade, it is frequently the practice tofill the body stock, i.e., the raw uncoated paper from the felting andsubsequent drying and smoothing operations, with an inert, white mineralfiller and to coat both sides of the body stock with a high brightnesswhite pigment, e.g., kaolin clays, in a binder of casein latex, starchor other adhesives to achieve a sheet opacity of at least 88 to 90% anda TAPPI brightness of 70%. The resulting publication grade paper stockhas a weight of 34 to 45 pounds per ream, a thickness of 3 to 4 mils,uncalendered, and a tensile strength of 3000 to 5000 p.s.i. for uncoatedstock.

OBJECTS OF THE INVENTION One object of this invention is to producethermoplastic films suitable as a replacement for paper having highopacity, brightness and tensile strength and low weight.

A further object of this invention is to provide thermoplastic filmssuitable as a replacement for paper which contain from about 2 to about60 percent of a treated inorganic filler in a thermoplastic material.

Still another object is to provide colored thermoplastic films suitableas a replacement for paper.

Yet another object of the invention is to provide fibrillated filledfilms.

SUMMARY OF THE INVENTION These and other objects are attained byincorporating into a thermoplastic material an inorganic filler whichhas been reacted with an organic derivative of ortho titanic acidcontaining at least two hydrolyzable groups, forming films therefrom andcold drawing the films under conditions which produce a white, opaquefilm of high brightness and tensile strength. To obtain colored films,inorganic pigments conventionally used as coloring agents, which havebeen reacted with an organo titanium compound containing at least twohydrolyzable groups are used or may be included with other organotitanium treated inorganic fillers. Alternatively, organic dyes may beincorporated in the organo titanium compound which is reacted with thefiller.

The organo titanium compounds used to react with the inorganic fillermaterial are represented by the formula Ti('OR) 'R' wherein R is ahydrocarbon radical containing from 1 to 12 carbon atoms and R may be000 OR" or a hydrocarbon substituted silicic acid radical (OSi'R whereinR" is a substituted or unsubstituted hydrocarbon radical having from 1to 40 carbon atoms and wherein R" is a substituted or unsubstitutedhydrocarbon radical having from 6 to 40 carbon atoms providing that R'and R are not identical. In the formula m is equal to 2 or 3. At leasttwo hydrolyzable groups, preferably OR groupings, must be present in theorgano titanium compound in order that hydrolysis of the organo titaniumcompound occurs followed by its polymerization to produce a film oforgano-substituted titanium oxide at the filler surface. Through thisreaction the tiller is provided with a hydrophobic, organophilic film.

The organo titanium compounds can be prepared by reacting 1 mol ofTi(CR), with from 1 to 2 mols of a compound represented by the formulaAR wherein A is hydrogen or a group capable of reacting to remove an ORfrom the Ti(OR), molecule and R is as described above. A mixture of twoor more compounds of the formula AR may be used. The preparation ofillustrative organo titanium compounds is more particularly described inU.S. Pat. Langkammerers 2,621,193, page 15 of the E. I. Du Pont deNemours & Co. publication entitled Tyzor, Versatile Chemicals ForIndustry (1965, revised 1966) which describes the reaction product ofLangkammerers process as a monomer whose formula is identical to theTi(OR),,,-R., formula given above, but which also points out that themonomers are unstable and under certain conditions may decompose byreacting with one another to yield a polymeric reaction product of astructure identical to that shown in col. 4, lines 51-58 of theLangkammerer patent; as pointed out by Langkammerer (col. 4, lines40-42), the extract structure of this polymeric reaction product isunknown.

Reverting to the starting material Ti(OR) R may be selected from thegroup consisting of alkyl, cycloalkyl,

aryl, aralkyl, and alkaryl radicals containing from 1 to 12 carbonatoms. Specific examples of compounds represented by the formula aretetramethyl titanate, tetraethyl titanate (ethyl orthotitanate),tetrabutyl, tetraisopropyl, tetraamyl, tetraoctyl, tetradodecyl,tetra-Z-ethyl-hexyl,

tetrabenzyl, tetraphenyl and tetrabetanaphthyl titanates.

The radical R" mentioned above represents a hydrocarbon radical havingfrom 1 to 40 carbon atoms taken from the group consisting of alkyl,cycloalkyl, aryl, aralkyl, alkaryl hydrocarbon radicals which maycontain various substituents such as halogens, e.g., a perfluoro methylradical, hydroxyl groups, keto group (radical of levulinic acid) amino,nitro and heterocyclic groups. Examples of R" groups are methyl, ethyl,propyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, octadecyl,cyclohexyl, cycloheptyl, phenyl, naphthyl, tolyl, xylyl, benzyl, phenylethyl, chlorophenyl, dibromophenyl, 2,3-dihydroxy propoxy. The varioushydrocarbon radicals may contain aliphatic unsaturation as well asaromatic unsaturation. Perfluoro compounds may be used. R' is of similarscope but with exclusion of radicals containing 5 or less carbon atoms.

A preferred class of compounds represented by the formula AR are theorganic aromatic and aliphatic carboxylic acids. The resulting organotitanium compound may be called an ester carboxylate or an esteranhydride of ortho titanic acid. Among the aliphatic and aromaticorganic acids that may be used are straight or branch chain, saturatedor unsaturated, substituted or unsubstituted monoor poly-carboxylicacids including such acids as stearic, palmitic, ricinoleic, linoleic,lauric, myristic, oleic, benzoic, caproic, caprylic, nonylic, capric,linseed oil acids, castor oil acids, tall oil acids, cocoanut oil acids,soy-bean oil acids, tung oil acids, perfluorooctanoic acid, phthalicacid, adipic acid, etc.

A second class of useful compounds which generally will be used inconjunction with one of the acids cited above, although they can be usedas sole component of the reaction with the Ti(OR) are the organicalcohols or organic phenols. Among such compounds are 2-phenoxyethanol,m-cresol, diethylene glycol, 2,6-dioctadecyl cresol,l-(2-pyridylazo)-2-naphthol, naphthol, anisyl alcohol, glycerol,geraniol, etc.

In some cases the combined effect of the two classes just cited may beobtained by using an ester such as the triglyceride of ricinoleic acid.

The inorganic fillers of this invention comprise fillers in particulate(of any particle size distribution and any particle shape) or fibrousform. As long as the inorganic filler contains at its surface reactivehydroxy groups and/ or about 0.1 to about 2 weight percent based on thefiller of adsorbed water, the specific chemical nature of the filler isnot important. Suitable inorganic fillers include clay, calciumcarbonate, barium sulfate, glass in the form of fibers or thinplatelets, vermiculite, asbestos, mica, etc. If a colored product isdesired any of the well-known inorganic coloring pigments may be usedincluding iron oxides, Prussian blue, zinc chromate, cobalt blue,ultramarine blue, etc. All of these materials generally have theproperty of being chemically inert to the polymeric materials and arerelatively heat resistant as compared to the polymeric material.

Clays are a preferred inorganic filler because of the superiorproperties of the treated clay of our invention in comparison with theuntreated clay, the ready availability of clays and their relatively lowcost. Illustrative clays are untreated or treated (e.g., calcined ordelaminated) English or Georgia filler and coating clays. Clays arecomposed of two atomic lattice structural units. One consists of twosheets of closely packed oxygen atoms or hydroxyl groups in whichaluminum (and occasionally iron or magnesium) atoms are embedded inoctahedral coordination. The second unit is built of silicatetrahedrons, being arranged so as to form a hexagonal network, which isrepeated indefinitely to form a sheet-like structure. In kaolinite, thestructure is composed of a single tetrahedral sheet and a singlealuminum octahedral sheet combined in a unit so that the tips of thesilica tetrahedrons and one of the layers of the octahedral sheet form acommon layer. The aluminum sheet, in a unit cell, carriers six hydroxylgroups, which appear on one stltf'stt 9f the cell and two hydroxylgroups which project toward the center of the cell. The structuralformula can be represented by '(OH) Si Al O Clay minerals thereforecontain hydroxyl groups which can be pictured as potential reactionsites. Clay minerals are also very finely divided and have surface areasvarying from about one square meter per gram up into the square meterper gram range. Like all finely divided and fibrous materials water isgenerally adsorbed onto the clay particles in very small amounts and canserve as a reaction site.

The inorganic filler-organo titanate products are formed by dissolvingthe organo titanate in an anhydrous organic solvent, wetting the surfaceof the inorganic filler with the solution and maintaining contactbetween the two materials until reaction is completed. Generally thereaction occurs spontaneously but, in some cases, gentle heating isrequired to speed the reaction. The solvent and hydrolysis products arethen removed by distillation or filtration. As a result of thistreatment it is believed an extremely thin layer of an organicsubstituted titanium compound or hydrated titanium oxide is formed byhydrolysis of the titanium compound on the surface of the inorganicmaterial, due to the presence of hydroxyl groups in the inorganicfiller, e.g., in conventional clays, or due to the presence of a traceof adsorbed water. Whatever the mechanism the product is stable tofurther processing conditions.

The amount of organo titanate, Ti(OR) R' used will vary from about 0.5to about 6 weight percent based on the dry weight of the inorganicmaterial, the amount used being partially dependent on the surface areaof the inorganic material since it is essential that substantially allof the surface area be reacted. The organo titanate should be dissolvedin a solvent which does not react with the titanate. Such solvents arehydrocarbons such as naphtha, hexane, octanes, etc. and chlorinatedhydrocarbons such as trichloroethylene. The solvents should beanhydrous. In the event that the organotitanium compound is volatile theinorganic material may be directly reacted with it by passing thegaseous material across the inorganic surfaces. The volatile organotitanate may be diluted with a dry inert gas to facilitate this process.If the inorganic material lacks reactive hydroxyl groups at its surfaceand has been subjected to severe drying conditions, it will be necessaryto mix it with water such that its surface contains from about 0.1 toabout 2 weight percent of water prior to the reaction with the organotitanate.

The particle size and shape of the inorganic material is important onlywith respect to the end use of the filled polymeric composition. Thus, avery fine particle size may be desired when the polymer composition isdrawn to produce films of 0.5 mil thickness.

The inorganic filler-organo titanate products used in the invention areset out and claimed in the commonly assigned application of Horton H.Morris and I. P. Olivier, viz., Ser. No. '872,730, filed Oct. 30, 1969,now issued as US. Pat. 3,660,134.

The thermoplastic polymers of our invention cover a variety of types.Any thermoplastic polymer can be used, the term thermoplastic as used inour application applies to synthetic resins that may be softened byheat, and then regain their original properties upon cooling. It is notintended that the polymer be void of any crosslinking. For example,impact polystyrenes which contain crosslinked rubber can be used.

An important class of polymers are those obtained by polymerizing orcopolymerizing organic compounds containing a carbon-carbon double bond.Such polymers include the polyalkenes formed from monomers such asethylene, propylene, butylene and isobutylene; the polydialkenes formedfrom monomers such as butadiene and isoprene; the halogenatedpolyalkenes from monomers such as dichlorodifiuoroethylene, brominatedethylenes, tetrachloroethylene, chlorotrifiuoroethylene, andtetrafluoroethylene; the vinyl resins such as polyvinyl acetal,polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinylformal, polyvinyl carbazone, polyvinyl chloride and polyvinylidenechloride; the polystyrenes formed from such monomers as butadiene,substituted butadienes as isoprene, styrene, alpha-methyl styrene andthe chlorostyrenes; and acrylic resins formed from such monomers asacrylic acid, methacrylic acid and the esters and nitriles thereof suchas methyl acrylate, ethyl acrylate, methylmethacrylate, acrylonitrileand methacrylonitrile. Another related group of resins include thecopolymers and terpolymers of the preceding monomers. Examples arecopolymerized butadiene-styrene, vinyl chloride-vinyl acetate, vinylchloride-vinyloxyethanol and ethylene-maleic anhydride.

-.An additional class of thermoplastic polymers are condensationpolymers such as the nylons and polyurethanes.

Preferred polymers are those synthetic polymers of monoethylenicallyunsaturated monomers containing two to six carbon atoms and especiallythose polymers and copolymers of ethylene or propylene and othermonoethylenicaly unsaturated monomers. Polymeric compositions useful inthis invention are included among the polymeric compositions disclosedin the commonly assigned application of Horton H. Morris, J. P. Olivierand P. I. Prescott, viz., Ser. No. 872,752, filed Oct. 30, 1969, nowissued as U.S. Pat. 3,697,474.

The compositions of this invention are prepared by simply mixing thepolymeric material with the treated filler using any of the conventionalmeans common to the plastics industry. Thus, the polymer may be mixed onroll mills at elevated temperatures until soft and the dried filleradded during the milling action. Alternatively, the polymer and fillermay be mixed together in ball mills, dough mixers with or without addedsolvent and other conventional additives such as plasticizers,antioxidants, lubricants, dyes, etc. Thereafter, the compositions areextruded in conventional apparatus at elevated temperatures to formfilms having any desired thickness. These films then may be reduced inthickness in two steps, the first occurring immediately after the filmemerges from the extruder before it is quenched on the chill rolls adnthe second occurring after the film has cooled substantially below 100C. In the first reduction in thickness of the film, the film remainstranslucent. In the second step, the thickness of the film is furtherreduced and becomes white and opaque. For example, in the firstreduction the film thickness can be reduced to 1.5 to 5 mils while inthe second step, the film can be further reduced to 0.5 to 1.5 mils.However, the opaque films of our invention may have a thickness of asmuch as 5 mils. The opacity of our films is due to the production of amultitude of tiny voids produced during the cold drawing step. Suchfilms are in contrast to the compositions disclosed in the commonlyassigned application of Morris, Olivier and Prescott referred to above.In that application, any films produced from the compositions havecomparatively few voids in comparison to the films of our invention.

The second step, which can be termed the orienting operation (althoughorientation does occur in the first reduction), may be performed onconventional apparatus or by hand. Alternatively, the compositions maybe merely conventionally drawn and oriented at a conventionaltemperature, for the first drawing step, to directly produce atranslucent drawn film, followed by drawing said film at a temperaturebelow that temperature at which the film remains translucent to producean opaque film of about 0.5 to about 1.5 mil thickness.

The temperature of the drawing steps will depend on the particularpolymer being usid. The first drawing step is carried out attemperatures that produce a translucent material. The second step may becarried out at temperatures from room temperature, i.e., -30 C. up tothe temperature at which opacity fails to appear. In general, thetemperature for the second step should not be above 100 C. although somepolymer compositions might be *6 drawn at slightly higher temperaturesand still yield an opaque product.

The films of this invention can have a 7 to 16 pound weight per ream permil of thickness, or can be made as low as 7 to 8 pounds per ream. Theyhave been prepared in thicknesses ranging from 0.5 to 1.5 mils dependingon the thickness of the undrawn film and on the temperature at which thefilm is drawn. The brightness of the films is at least 70% and can beimproved to about 97% as measured on an automatic color brightnesstester (Martin Sweets Company). The fihns have a tensile strength of25,000 to 27,000 p.s.i. which is far above that of conventionalcellulosic paper. They are thus stronger, thinner and lower in weightthan cellulosic paper, whiter than conventional publication paper andeven in the 0.5 mil thickness can ha ve the same opacity. The films havea glossy surface.

The films of the invention which can be called ultrathin paper areparticularly valuable as publication paper since their low weight willreduce postal rates and their thinner sheets will reduce bulk. The filmsare also useful in other applications where high strength, opacity andthinness are desirable such as in top liners for paperboard, breadwrappers, plastic bags for packaging or garbage disposal and otherwrapping, covering or containing uses. They may also be furthermodified, as by surface oxidation, to improve their receptivity.

The films of the invention may also be used in capacitors. A perennialproblem with capacitors is the degradation of the chlorinated organicdielectric fluid. The degradation products are the cause of prematurecapacitor failure which may be prevented or at least delayed by using aplastic film containing a filler active sites which will serve toscavenge the degradation products. The organo substituted titanatetreated clays in the ultrathin paper will remove impurities and thepaper because of its open surface structure will tend to promotemigration of the dielectric fluid.

The films of the invention can also be machine fibrillated to produce anopen net-like structure. The edges of the fibrillated film have t'myfibrils which act to hold a chopped staple, made from the fibrillatedfilm, when made into a non-woven sheet. The fibrillated film may be usedin laminates, non-woven fabric, rug backing and other applications wherethe mesh structure is filled, coated or impregnated.

The following examples are given in illustration and are not intended aslimitations on the scope of this invention. All parts and percentagesare by weight unless otherwise stated.

EXAMPLE I (a) Triisopropyl monooleic titanate was prepared by mixing 258grams (0.91 mole) of tetraisopropyl titanate with 256 grams (0.91 mole)of oleic acid at room temperature accompanied by stirring. The mixturebecame warm immediately indicating the occurrence of the desiredreaction, and was allowed to stand for several minutes. The product wastriisopropyl monooleyl titanate dissolved in isopropyl alcohol. Withoutremoving the alcohol the product was mixed with 50 pounds of naphtha toproduce a low viscosity solution containing the titanate. Thereafterthirty pounds of a fine particle size delaminated kaolin was addedslowly to the naphtha solution accompanied by vigorous stirring toprevent lumping of the clay. After complete addition of the clay to givea 3 8% solids dispersion in naphtha, the mixture was stirred for anadditional half hour. The dispersion was then dried to remove naphthaand isopropyl alcohol and the product therefrom was pulverized. Theproduct did not appear, on visual examination, to be any different fromthe original kaolin.

To determine the effect of the treatment of the clay with the organotitanium derivative 3 grams of the OX-l and 3 grams of the untreatedkaolin were separately shaken vigorously with 15 grams of water in atest tube. The tubes were then allowed to stand until the kaolin eithersettled to the bottom or floated on the surface of the water. The amountof OX-l which settled out, as determined gravimetrically, was less than0.1 percent showing that OX-l was hydrophobic whereas all of theuntreated kaolin was wetted by the water within seconds of the standingperiod. When the OX-l was added to an organic solvent such as toluene,it dispersed therein readily and completely in contrast to the untreatedclay which balls or gums up in toluene.

(b) Three hundred and fifty grams of polypropylene having a melt indexof grams per 10 minutes at 230 C. were banded on a rubber mill betweenrolls heated to 360 F. and mixed thereon for about 15 minutes. Onehundred and fifty grams of OX-l were then slowly added and milling wascontinued for another 15 minutes. The composition thus formed wasremoved from the rubber mill, cooled and granulated. The composition didnot stick to the hot rolls and was easily removed therefrom. To insurecomplete dispersion of the OX-l in the polypropylene the composition waspelletized by passing it through an extruder equipped with one 40 meshand one 250 mesh screen at a temperature of 260 C. into a cold waterquench bath using a die which produced a A; inch rod. The cooled rod wasthen pelletized and dried in a vacuum oven at 100 C. The pellets werethen extruded through a slit die adjusted to produce a 5 mil film. Thefeed zone and the metering zone on the screw were heated to 245 C. andthe die was maintained at 238 C. The film was extruded at a constantrate onto a cold quench roll revolving at a controlled circumferentialspeed. By changing the circumferential speed from 7 to 11 and then to 16feet per minute films were produced having thicknesses of 3, 2 and 1 milrespectively. The films thus produced contained 30 weight percent oftreated clay, and were slightly yellow and translucent.

The 1, 2 and 3 mil films were oriented at a temperature of about 23 C.to produce white opaque thin sheets, having the properties shown inTable I as compared to the properties of the undrawn film.

TABLE I Undrawn film Measurement Drawn film Color purity, percent Visualefliciency, Percent.-- Brightness, per

Tensile strength, p.s.i 25, 000

Using the same technique shown in Example I(b) and the samepolypropylene, 3 mil films were prepared containing 10, and weightpercent OX-l. The films were then machine drawn at a 9 X ratio at anoven temperature which was set at 135 C. to give white opaque films.(The oven was 10 feet long and the film was drawn after it had gone onlyone foot into the oven. The entry speed of the film into the oven wasabout 20 feet per min ute. The exit speed of the oriented film was 190feet per minute.) Part of the composition containing 30% OX-l wasfibrillated as it was drawn and had a net-like structure. Scanningelectron microphotographs show that the cut edges of the fibrillatedfilm contain discrete fibrils.

EXAMPLE III Two compositions were made from a polypropylene having amelt index of 6.5 grams per ten minutes at 230 C., one containing 20 andthe other 30 weight percent of OX-l. The compositions were extruded, asshown in Example I(b) for production of translucent films, to obtain a 5mil, slightly yellow and translucent film. When this film was hand drawnat room temperature ca. 20- 30C., it became white and opaque and had atensile strength of 25,000-27,000-p.s.i.

EXAMPLE IV To obtain colored ultrathin paper three different inorganicpigments were reacted with the reaction product of tetraisopropyltitanate and oleic acid in the same manner as the clay was reacted inExample I(a). Thirty grams of each treated pigment were added to apolypropylene having a melt index of 4.0 grams per 10 minutes at 230 C.on mill rolls and then 70 grams of OX-l were added. The compositionsthus produced were extruded into thin films and the resultant films colddrawn at about 23 C. to yield colored opaque 1.5 mil film. The firstpigment used was a synthetic iron oxide known as Mapico Yellow Lemon ofColumbian Carbon Company. The film prepared using this pigment wasyelloworange in color. When a zinc chromate known as C.'P. Zinc YellowImperial Color and Chemical (Hercules Powder Co.) was used the finalfilm was a bright pastel yellow and when a basic lead chromate depositedon a silica core known as Oncor M 50 of the National Lead Co. was usedthe final film was a light pinkish orange.

EXAMPLE V Four hundred grams of polyethylene having a melt index of 2grams per minute at 125 C. were bonded on a rubber mill between rollsheated to C. and mixed thereon for about 10 minutes. One hundred gramsof OX-l were slowly added and milling was continued for another 15minutes. The composition thus formed was removed from the rubber mill,cooled and granulated. The granulated composition was pressed betweenplatens heated to C. to produce a 6 mil thick film. The film wastranslucent as pressed. However, when the film was drawn, by hand, atroom temperature (23 C.) it became white, opaque and 2.5 mil thick.

It is obvious that many variations may be made in this invention withoutdeparting from the spirit and scope thereof as defined in the appendedclaims.

What is claimed is:

1. A process for producing an opaque and glossy film having an opensurface structure which comprises drawing a polymeric composition at atemperature which produces a translucent film and thereafter drawingsaid translucent film at a temperature below that at which the filmremains translucent to thereby produce said opaque film, said polymericcomposition comprising a thermoplastic polymer having incorporatedtherein an inorganic filler the surface of which, prior to the incorporation step, have been reacted with an organo titanium compoundcontaining at least two hydrolyzable groups and which is represented bythe formula Ti(OR) R wherein R is a hydrocarbon radical containing from1 to 12 carbon atoms and R is OCOR, OR', or OSiR wherein R" is asubstituted or unsubstituted hydrocarbon radical having from 1 to 40carbon atoms and wherein R is a substituted or unsubstituted hydrocarbonradical having from 6 to 40 carbon atoms providing that R and R are notidentical and wherein m is equal to 2 or 3, and wherein said inorganicfiller prior to reaction with said organo titanium compound contains atits surface either adsorbed water, in an amount ranging from about 0.1to about 2 percent, weight percent based on the filler, or reactivehydroxy groups or both reactive hydroxyl groups and said adsorbed water,whereby the hydrolyzable groups of said organo titanium compound arehydrolyzed by said adsorbed water or reactive hydroxy] groups, or both,to produce a polymeric organo titanium compound at the surfaces of saidinorganic filler.

2. A process as in claim 1 wherein the second drawing process is carriedout at temperatures of from 20 to 100C.

fibrillated during the final drawing step.

References Cited UNITED STATES PATENTS 10 JAY H. WOO, Primary ExaminerUS. Cl. X.R.

155 Unwsn STATES FATENT owes CERTFFICATF @F CQRREQHfiN Patent No. 3,h,937 Dated April 16, 197

Inventor g Horton H. MOIIiS, et a1.

It is certified that errof appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column line 31, delete "the";

Column Column 2, line 25, "OR' should be OR 2, line m, "CR" should be ORColumn line, '46, before "page" insert. --[see also Column 2, line 58,after "unknown insert --3 Column 5 line no, "adn" should be and --g'Column 5, line 68, "usid" should be used ---5 Column 9 line- "hydroxy'"should be hydroxyl si ned 21nd sealed this 10th day of September 19m,

(SEAL) At'test:

M12601 M, GIBSON, JR. C. MARSHALL DANN attesting Officer Commissioner ofPatents

